MOLECULAR ORBITAL THEORY .

CMO -

T)

# It is based on wave

nature of electron .

# nature
It explains paramagnetic
Oz molecule
of
.

* can determine
Using MOT ,
we

bond relative
relative
length order
,

stability order , bond order

of diatomic molecule lion .

( can be Mononuclear / Metro nuclear

diatomic molecule ) .
postulates
→
of Mo T
-
!

① As in atom electron are

present
in various atomic orbitals ,

similarly in molecule electron are

in various molecular orbital

present
.

② In atoms e- revolve around

one nucleus ,
hence it is monoclinic ,
but in molecules electron revolve

around more than one nucleus

to it is polycentric .

③ Molecular orbitals are formed

atomic orbitals atom
when
of 2

to linear
combine according
combination
of
atomic orbital method
( L -
C A O
-
-

④ Electron in various molecular orbitals

 awarding to Hund 's Rule ,
is
filled
Aufbau principle , parulis exclusion

principle .

L-CA0Meth

There are
different types of
molecular orbital .

① Bonding molecular orbital CB -

mo) :

is It has energy lower than pure

atomic orbital which combine .

( BMO is more stable)

ii) Formed due to constructive

interference .

iii) Ft is involved in Bond Formation .

② Antibonding molecular orbital CABMO)

i) It has than pure
energy more

atomic orbital .
Ci -

e less stable ) .
ii) It is formed due to destructive

interference .

iii) It is not involved in bond

formation .

③ Non
Bonding molecular orbital :

when e- wave two atom

of
combine with Same phase or

different phase Simultaneously then

molecular orbital is
non bonding
formed .

Energy of
Nonbinding molecular = Atomic orbital
orbital
 Interference Addition or subtraction

of two waves .

molecular
overlap ) Binding
f) ( tve
orbital of AB
p molecule
'

a) constructive Interference :

#mq2vavex = Ya -14,
Y
# BMO

€
A -

Y.
Resultant amplitude
increases
amplitude of e-
4A =

ie
probability of
wave atom A
of
( Atomic orbital A,
binding e- between
of
nucleus Increases
BM O is formed
YB
- .

=
amplitude of e-
B
Amplitude a probability
Wave
of alum
( given by of finding
( atomic orbital e-
of B)

Years , = Bonding molecular orbital of mollusk

Ape
 P C -
re overlap )
b) Destructive Pmterfeoenu :

( subtraction 2 waves
)
of

VA # ABMO

If
Phase
y*nm
YB # Resultant

amplitude lvses .

ie probability of e-

between nucleus Ise

A-Bmo is formed

4ft =
Antibonding
orbital
molecular

molecule AB
of
.

( more
Energy ,
less

stable
As Repulsion between bonded nuclei

Tsu due to pour screening

( as lvses )
-

e probability .
 Energy level diagram .

No molecular orbital formed

of
-

No atomic orbital combined

of
=
.

^ 1-7
Y*ABlA'BMo )
.

i
-
.
i
r e
'

qnersy r
-
. n

17 17
'
i
- -
.

i I
- -
- -
- - - - - - - - -

.
'

,
/ same or

I Same
nearly
'

M
.

'
-
energy
-
r
- .

HAB
( BMO )

HAB =
Bonding molecular orbital of molecule AB .

YA = Atomic orbital of atom A

Atomic atom B
YB = orbital of
Y*mz =
Antibonding molecular orbital of molecule AB
 Condition for 1. c. Ao .

① combining Atomic orbital must have

same or
nearly same energy .

② Atomic orbitals can combine either

the molecular axis

along or

to molecular axis
perpendicular .

( z axis considered as molecular Axis

③ Different direction orbitals cannot

combine .

ey_ Px will not combine with Py / Pz .

④ Overlapping region should be high .

 Axial overlap → Along Molecular Axis

H
r bonded molecular orbital is formed .

Combine
→ ABMOCXT)
(out of phase, ( High Energy)
A -

o + A. o

B -

M -

O
( Tn Phule )
( low
Energy
plane
→ Nodal

!
of M o
- -

±i•
out of .

+
' '

. g-
* IS

CABMO )

µ, is, ¥9
d) In which orbital as Artis
Nodal plane is present No nodal qs.no,
AI
'

plane
2 dimensional plane
Nodal plane →
Imaginary
-

where probability of finding electron is zero

.
 plane
→ Nodal

!
of M o
- -

'
* . .

+
"

ET i g-
* 25

CABMO )
25 ) KS)
↳

( No Nodal plane vi. no

,

¥:÷÷
.
( ABMO)

e. no

52192
f ,
(B -
MO)

NO .
nodal plane
in Mro .
 Lateral Overlap It to molecular Axis

Is it bonded molecular orbital

is formed .

→ Nodal plane

-1.8!!
T T
D
±mY
>
D
- -

man ,
• •
Cudesthvhre plane
0 f) interference)
*NYwp*zpy )
2Pa
or

spy
2132C
or

2kg
LIE ,
1-
Ott
Constructive
- .
-

( interfered
ttnodal
1T2P×
plane

or
Bi④
( lT2py ,
Cli) which molecular
bonding orbital .

has Nodal plane ? Ans →

⇐ gon Hay)
Q2 ) which molecular orbital have maximum

( or two ) Nodal plane .

Ansi tT*spx /IT*zpy .

 Energy order of various molecular
orbital .

( Experimental order )

Casey If total E E 14
:
no
of
. .

( s a p mixing occur due to small

energy gap)

or Is < THIS cr2SCr*2SLIT2Px=IT2pyLr2pz

-

degenerate
<
T*2pz=IT*2py L r*2Pz orbital

d¥e
orbital .

dlgeneral orbital → Equal energy

§ orbital .

↳ electrons
filled all .

to Hund 's Rule

-

case 2: total e-
If no
of 7 14
.
.

C S K p does not occur due to

mixing
large energy gap between 25 and 2p)

rise o* IS C ✓ 25 Cr*2S L r 2Pa L IT 2Pa = IT

2Py

C IT*2pq = IT '*2py < r*2Pz .

 Energy level diagram
-

① Sum
of e- E ly Clase -
c
)

^
④ =

,
¥pE '

-
.
.

II
.

II
-
'

- -

I
TIME itxipy
" "
a .

52172

I II

¥
. .
. .

I
monomolecular
mini
Fi
M
A -0 I A. o .

Mo
② Sum e- 7 14 ( case 23
of
-

,
¥pE '

.
.
.

II
.

II
-
-

- -

#÷%I*zp
I '
'

i'
, itxipy -

21' in .

.
II .
.
-
-

-
up
-
.

ITV2 ITZPY
.

-
-
.
-

-
'

. -

.
.

m.awm.cm.
I
monomolecular
mini
'
?
M
A -0 I A. o .

M O
 Bond order :( B -0) :

↳ It is total covalent
no
of
.

bond between two atom

specific
.

For diatomic molecule

( Nb =P
B- 0
1-2 Na )
= -

or diatomic Ion .

Nb total e- in Bonding molecular

→ no
of
.

orbital .

Na → total no .

of e- in Antibonding
molecular orbital .

B- 0=0 species does Exist

If → not

under any condition

If B- 0 = ( Fntegral value)
→ Species Exist and
=
1,2 , } . .
.

is stable .

If B- 0 = Fractional → Species exist and

stable law to MUD

Bond order a Bond
strength
Bond order a Bond
Energy
Bund order a
stability

2 1-
Bond order
Bond length

Bund length a 1-
Bond strength

paramagnetic species → Having atleast one

un pair e- .

Diamagnetic species →
Having all
paired
electron .
O ) find O -
O relative Bond length
order and give its magnetic Behaviour

022T
't
02 OI 022
-

, Oz , , , .
 Him .

1) 02+0 = 16 -

I =
zm .

↳ cease
-4

Electronic configuration of 02 :

"

• IS r* Is
'
✓ 25 ✓
*
252 ✓ 21322

T2P2x = ttzpy IT
*
2Pa
'

↳ one unpaired Electron

.
'

.
0z④ is
paramagnetic

Nb
'

= Iue ,
Na = 5- e-

B -

O =
I (10-5) = 2.5
 Oz
-

# =D Ice

E -
C : risk 5*152 0252 0*252 621022
'

11-2%2 IT
y
'
iT*zp ,
! Itxzpy
H
2 unpaired e-

-
i. Oz is paramagnetic

B o
Iz ( IO 6)
-

= -

B -

O = 2

i④
# 02-0 =p lbtl = Ite
-

( total E)

EC :
- 152 5*152 6252 r* 252 rzpz2
-52139 HUF IT*2pfe IT
#
zlpy
H
020 paramagnetic
-

s
'

.
one unpaire
-­
 Bro (
Lz
=
to -

7) = I -5 -

ft 02240 = lb -
2 = 14 e-
→ case ( I )

✓ 152 6*152 • 252 6*252 IT 283cL IT

2

521722 -

z, No un pair e-
-
:
Diamagnetic -

B
-0=12 ( 10 u) =3
-

022
-

IF =
16+2 = 18 e- →date 2)
- -
-
-
-

5152 r* 152 ✓ U2 g*zg2 rzpzt lT2px2tT2py

IT
# 2135 Mvp}

e.
→ No unpuir

022
-

: → Diamagnetic
=
B- o =
Iz ( so -

8) =
①
=
 B
02 2

④
02 2-5

④
022 3

02 1.5
-

02h
-

Bmd
length co -
o) order

022 02-0 02
④
7 Og
-

7 7 7 02

1-
(Bond length a
)
Bond order
Q2) Find Bond orders magnetic nature

of species and predict whether

exist
they or not .

① Hz ② Bez ③ Liz

*
④ Cz ⑤ NL ⑥ Nez

*
⑦ Bz
Solution .

① Hz 2e
-

ex

r1S2 r*lS° . - - -

B- o =
I ( 2 -
O) = 1 one r bond

112 → Exist and diamagnetic

② Bez as 2143 = 85

5152 r* 152 • 252 6*212

B- o=
Iz ( y -
4) = O

Bez → does not Exist

③ Liz be
-

=p 213 ) =

oys2 6*152 -252

B- 0= bond
Iz (
one
U 2) I r .

-
=

↳ lie Exist and diamagnetic

④ Cz 2lb )
-

=
=
12 e

rise r
't
152 ✓ 252 0*252 ¥lT2py①
130=1218 -

4) = 2

Cz Exist a
diamagnetic = c

ACU to M o T bom bond CL

of
-
-

is it bind a it exist
in vapour phase
⑤ Nz =p 217 ) = the

g) S2 r
't
152 6212 6*252 IT 2pz2

IT 2 15221T bond
My rzpzz

B- O
I (10-4) 3
= =

Exist and is stable

Nz →

N EN

↳ one r & 2 I bind

⑥ Nez = 240 ) z 205

0152 r# 152 ✓ U2 oH2j2 521022

r*epz2
' # '
Input Tupy iT*2pz2 IT
spy

B- o= 1070)
Iz ( =

=
O

Nez does not Exist

-
⑦ Bz =p 215 ) = toe
-

rip 6*152 rut 8*252 Tmz' THI

B o =
I (6-4) = 1
-

Bz stable and Exist in vapour

phase
↳ Cz unpaired
paramagnetic

↳ one it bond is between

present
B -

B -
 /

3) Give Relative stability order :

D Hz Hz④ He
-0

Sturm

Hz =p 2e
-

=p
- 152
B- 0=+212032 I

Hz①
'
rls
-

ie

13-0=12 ( to> = O -
5

the -1526*15 '

3. e-

B- O=
Icu ) e 0-5

Bond order a stability

-

H2 ④ -0 ( stability corded
7 Hz 7 Hz
IF#
# have
If two or more
species
equal bond order them that

species will be more stable

which has less electron

no
of
.

in Antibonding molecular orbital .

Similarly ?

µz④ > NZO # 141-1=155

( stability order )
µ

, ↳, ,u}
14-1=135

,*,yqq,*z
a, ,

0*252=2.5
B
tzc 150252
'
O
as of
)
=
-

g - u

542,2 54722 TMZ

IT 't2pyz '
yet in ABM O -

B
0=12 (10-5)=25
-

AB M
-
O
5 e- in
-
 I

Q) Give correct relative H -

H bond

length order Ha , 112+0 , the

solution : Hz Hz⑦ 1720

-

t t t

B- 0=1 B- 0=0-5 B- 0=05

' ' '

5152 sis ots #s
t,
AB M o
-
- -

correct order
of Bmd length ,

④
H2O 7 Hz 7 Hz

f¥alBmd order

e- in ABMO

destabilise the im

due to which B E
-

becomes less

<
'

.
Henk Has more Bund length
=

1-
Bund length a
Bond Energy .
 sidecar
Fitbit

tismetiliiililiiiiititititititil
I

shortcut table for Bund order

-

Metro diatomic molecule :

④
1) NO →
( 7- 8) I
-

f- -
= me

'
• 1526*152 out 6*282 Muppet mpg
r2pz2

Lz (
B- 3
o =
10 -

y) = .

2) CO =D (6+8) = ly e
-

↳ oys2 EX 152 6252 't

252 IT2px2
'
r
Itzpy
621722 B -

o = 3
=
 Tusuelechronicspeiiesi

# Species having same number

electron is called isoelectronic

of
Species .

# isoelectronic species having Same

Electronic configuration ,

i .
have same value
of bond
order .

EI
2- 2④
i) NOT ,
Nz ,
Cz ,
02
H H H H

IUE
16-2=145
IUE 121-2

Hye
-

All have Same E -

have
binders
'

- - All same
 ④ -0
② CO ,
Nz④ ,
Cz

H H *

12-11=13
IU -
I ly I-

e- 3 e- =D e-

d t t

2¥ B- 0=2.5 B 0=2 S
-

BE
- - -

B -
o =3 .tw)
Ml isoelectronic species
Henie ,
not
have
Co① is does
order
Bond

=
an
Exceptional ehual
case .

QD Give Relative C -

O Bond length order

¥)
" ④
coz CO co 0
, ,

Solution:

rc←{
CO → Bond order = 3 u
D
④ Bo -

It but
CO
-

use MO 'T → Bond order =3 s -

, no
go
-

( 032 Bond order I -33

# }
-

→ = =) t =

$ 2132

Polyatomic ( use Resonating structure concept)

 coz
' -

> CO > COTO ( C -

o Bond

length order
)

02) Give relative o -

o Bund length
order .

11202 ,
Nantz ,
Koz

Sn :

17202 022 130=1

-

Tse -

Nazoz 022 B -0=1

-

=D

187-1
-

K Uz =D 13-0=1.5
-
Oz
D- e-
 - ← →

He In win.io?o?:n9a
ru ←
less -
recharge more - recharge

density density
less repulsion i. more
repulsion
Hh Bund length . . : more Bund length

Nazoz 7 Hzoz 7 Koz ( Bond

length)

Q 3) Find
paramagnetic species .

A) Koz b) At Oz ⑨ c) NOZ

added
) 02
#
2 unpnir e- ( Morts paramagnetic
unpueir
one
Paramagnetic
µ
K Oz
↳ paramagnetic
→
It
185
+
⑥
aa.lom.at
→ B- 0=1-5

one anpair e-

-
paramagnetic

AI0z④
↳ diamagnetic
→
-
AP④t0→ 185
13-0=1
zero impair e-
toe
-

act .

to Mo
-

t
h
# o T
-

↳ Applicable for diatomic

molecule / diatomic icon .

For
polyatomic
↳ to get Bond order use,

B- o =
total
specific
no
-

of
bonds between 2

atumgaur.SI
total R S
of
.

no
-

B- u= It nu bond
g
'

it

involved in
Resonance
 Dipole moment ( µ)

St S -

A 7- B CEN of B > A)

↳ polar wralmt bond

↳ such molecule called dipole
molecule

↳
.

Strength of electric dipole

is measured in terms
of
dipole moment
.

↳ Dipole moment is vector

quantity
.

↳ Represented tail .

Head
→
as →
.
A -
B
f t.

CE
-
N B > A) Less more E- N
EN

⑤
St S -

A -313
 /

Angular Triatomic molecule :

# nrcdipofm;:Yft
" '

O - Yi , ,µ ,
are

Mk
bond dipole
-

Tur = It ,
+ Ik

ful
u
r
-

1127 Ya 't 2MHz Wso

Tf Y, -_µz= X

yr =f¥µzwso
Mr #
'

2,42C It WSO)
c
. =

HWSO
=
I
2142€05 =2wsYE)
 |#
-

2X
Yr =
wtf)
Ff O Tsb

µp
cos
# dies
i -

Yr doses .

Bond length
#
.

/
drpo¥#
M d
#
q
.
=

molecule charged produced

of
due to
shifting
of e-

St 8-
A
;¥ ,
B
q①
unit
of dipole moment : e -
m
⑧
lomtmvnhy used is Debye CD,
esu.cm
 r

I D= 3.33 X 10-30 C. m

( Cwulvmb .
metre)

I E charge = I -6×10-19C
-
lo
= 4.8×10 es -
u .

Application .

D Xp = 0 ( Nonpolar molecule )

ID Xp f- 0 ( polar molecules

Mr = resultant dipole of
molecule .

#
Tm case of diatomic molecule lXkdbEN)
-

St 8- St S -
St S - St S -

Htt 7 Hta > HtBr 3h # GUD

EN 2 I 3 2 I 2- 8
2- I
y
- -
2h 2-5

1-9 0.9 O 7 o y
-

DEN -
# In case
of polyatomic molecule / ios

HR depends on

i) Bond dipole
ii) spatial arrangement Bonds
of
.

Cie arrangement of
bond in Space)
*
( use v. s -

E. p R -
for Shape )

Sw CC ) Csp)

u.s.e.pfy.pe
G- ① £02
= 2

lemur shape

lpcc) = 2 -
z

142 µ , 0
← →
=

OI C = O

H =
µz
liner shape ,

o
bond
Iz
-
g
XT
-

polar =

aiu
-

is

Ik -
th txt .
② Bfs ③ SF ,

↳ J
S -

N EB) = 3 ( Spy S NCS )

6CSp3dY
'

lp (B) =3 3
Ep
-

= 0
= 0

octahedral shape
Trigonal planar
.

Shape F

F
Ir
a First -

µ , if I,
←
My
B tf E -

f
n
-

.
F

¥443 F
Xk -

- o

Yu is resultant
of 1422143 If
Nonpolar
y, = My

5, = -

Ih

Yr
*
Nonpolar ,
but

B -
F bond is polar .
 EN CN
done pair dipole is alway
>
ng less than band

⑨ Nhs ⑤ Bres Phir dipole

j H
SN '- 4 Csp) she 6190392)
lp=1 hp ( Br ) -_ I

pyramidal shape .
Square pyramidal shape

#
"

"
adwianuesnisn i Br
atom
'
.

x'I
I Ianto
'
"
n
14 . ..

Cn H)
IF
polar compound
-

Iep
-

MI = +
Mbp
-
' MY
Fye ,
Hr FO N

¥¥ t%:*
↳ polar compound
- .

,
⑥ com He
is
-_
YI ,
-

step .

tho
←
fate H
Nonpolar
.
⑦ Pas FL

f- Cau - to Bent run,

Y
'

U
-
u
/
F
µR=O
¥
Nonpolar molecule .
⑧ Xe iz
=

Siva 5Csp3d)
Ip = 3

linear shape .

de Yk=o
l H
F Nonpolar

⑨ Xe
=
Ey

Sw = 6 ( Sp's d2)

Ip = 2

Square planar shape .

"
a
*

Nonpolar
 r

④ Nfs ④
'
④ a

slur -0

of
EN
" D
' ''

lie
v
*
Nonpolar
Etf #
ft
www.9I.is
-5in,
,

up
④ IT
↳ 1k¥01
ut
-
-

b
polar
 CN
"
④ in
④
④
I
' CN
on
N
N

←
:O -
u
µ
To
YI
"
's -
a ⑤ Csp
H
Hr tort M

✓
N
Nonpolar

-4k
to

polar compound
A) Gave correct order dipole moment
of

1) NB ,
NF3

2) Cuz -
F
, Utz -
U
, UB -
Br
, aye
u
IH k M
3) Tec CI
'
y
' w
d '
H

4)
Y en Y ya
c=c C - C

y
' '
u tf IH

"
din EE .
Go!
MB UB
a
a

Cl Orth lo) mefacm,

Para Cpj
 Q) Centre correct dipole
order
of
moment

7 ( Mk
1) MHz Nfz )

mnxmunarse emigh:
St S -

St S
-
St S St S -

Br AB
2) 43
-
F Uz -
U
43 - -
I

µ =
q
-
d
c-
cry
-

F >
↳
aza # Mr > 931 (
Expected,

Ctfu 793 -
F 743pm > CBI ( observed )

Mr =
qxd → Bond
length .

C -
d > > c-F CBmd length)

due to high bond

length of C-u w rt
-

C- F , dipole moment of Ayu is

Highest
.
3) isomers
O,
02
a) u n u a
\ l l
l
C = C C = c

mi
-
U H '
H

Trans isomer ( Cis -

isomers

( same group on ( same

group on same
opposite side) side)

O, 7 Oz

a 1-
Sina , Xp
O

cis 7 trans (XD

 "
b)
By it by ru
czc
C = C Oz to
ul
'
U '
/ H
H

( trans ( Cis)

( )
'

O, - O
( 02701)
Wirt A -

position 46 #
Ortho, trans
-

a
, > cis GUR)
position -315 # meta cm)
position -34 para ( p)
w

Dos=iw
'w
.

a
'

01=60
te
Ortho co) meth Cm)
para ( p)
-
diction benzene -

diction benzene -
di chlorobenzene

03702 701

YR ( 07 m > p)

-
-
 GB Az
U

d) d)
⑨ 0402=120 -
u
03=60
0=00
te '
O - Chin
m-
chloro
Pthlorotowiene toluene toluene

Q C 03 C Oz

93 ) Mr
-
y ( P s m > o

40
Toluene
#
 fT0determineofIoniccharau#
0fwvalentbm#
#

bond
' covalent
f
H - U

/
( covalent compound)

✓→ s, s -

Assume 1001 ionic H → U

HYO
*
? - U
get ,Y experimental
-
1814

get X theoretical
,

q f .

ti or C I units
q=
-

6022×10192
HExp I
Cf
'

d
l
q
-

Kexp = ⑧ d
d
.

Mineo =
q
-

14mW
= 1.6022×10-19×4 .
Fractional

Charge

Yo Ionic character = Heit .

X Wo .

Mineo
 the
OD the experimental value
of dipole
moment HU is l 0313 The bond
of
-

length bond
'
HU is I -275A
of .

Find Yo ionic character in H u - .

SEN :

Kexp = I -0313
= 1-03×3 -
33×10-30 C -
m

=
3 -
43×10-30 Cm .

tom
-

D= I' 275 A° = I -
275×10 .

H U
, q= l unit = 1.6022 x 1519C

Mineo =
q . d = 16022×10-19×1.275
X 10-10
= 2-04×10-29 Crm
= 20 n X -
10=30 cm

of . Ionic character =
Next xioo

Theo

=
3-43×-10-30 7100

20 -
U X 10-30
= 16 -

811 .

=
171 .
 x

Dipole moment is I -5 D
02 )
of .

×
the dipole moment
of
, -
× ×
×

A) I 5 D
- b) I D )
C 2- 3513 d) 3D .